全文获取类型
收费全文 | 9201篇 |
免费 | 1232篇 |
国内免费 | 740篇 |
专业分类
化学 | 6741篇 |
晶体学 | 122篇 |
力学 | 412篇 |
综合类 | 49篇 |
数学 | 838篇 |
物理学 | 3011篇 |
出版年
2024年 | 26篇 |
2023年 | 177篇 |
2022年 | 264篇 |
2021年 | 309篇 |
2020年 | 352篇 |
2019年 | 322篇 |
2018年 | 252篇 |
2017年 | 229篇 |
2016年 | 437篇 |
2015年 | 376篇 |
2014年 | 453篇 |
2013年 | 657篇 |
2012年 | 838篇 |
2011年 | 846篇 |
2010年 | 507篇 |
2009年 | 510篇 |
2008年 | 592篇 |
2007年 | 572篇 |
2006年 | 489篇 |
2005年 | 455篇 |
2004年 | 300篇 |
2003年 | 205篇 |
2002年 | 224篇 |
2001年 | 190篇 |
2000年 | 181篇 |
1999年 | 157篇 |
1998年 | 145篇 |
1997年 | 112篇 |
1996年 | 108篇 |
1995年 | 136篇 |
1994年 | 119篇 |
1993年 | 90篇 |
1992年 | 79篇 |
1991年 | 70篇 |
1990年 | 67篇 |
1989年 | 34篇 |
1988年 | 45篇 |
1987年 | 35篇 |
1986年 | 35篇 |
1985年 | 31篇 |
1984年 | 23篇 |
1983年 | 9篇 |
1982年 | 20篇 |
1981年 | 14篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
61.
Summary Preparation of cobalt(II) halide complexes with neutral bidentate ligands, including 2-pyridyl alkyl ketones, is reported. 2-Pyridyl alkyl ketones act as monodentate or bidentate ligands depending on the reaction solvent used. Tetrahedral complexes are isolated for all potential -donating neutral ligands.trans-Octahedral complexes are formed only if the neutral ligands are strong -donors and -acceptors. The stereochemistry of cobalt(II) halide complexes is discussed in relation to the nature of the neutral ligands. 相似文献
62.
Fernández-Varela R Suárez-Rodríguez D Gómez-Carracedo MP Andrade JM Fernández E Muniategui S Prada D 《Talanta》2005,68(1):116-125
The combination of attenuated total reflectance-fourier transform mid-infrared spectrometry (ATR-FTMIR) and multivariate pattern recognition is presented as a fast and convenient methodology to ascertain the source product an oil slick comes from and to evaluate the extent of its weathering. Different types of hydrocarbons (including crude oils, several heavy distillates and the Prestige's heavy fuel oil) were spilled on metallic containers designed ad hoc and their fate monitored by ATR-FTMIR. Not only environmental conditions were considered for weathering but artificial IR- and UV-irradiation. Pattern-recognition studies revealed that the different hydrocarbons clustered at different locations on the score plots and that the samples corresponding to each oil became ordered according to the extent of their weathering. Among them, fuel oil samples coming from the recent disaster of the Prestige tanker off the Galician shoreline showed a distinctive behaviour. Comparison of natural-, IR- and UV-weathering of a crude oil showed that IR solar radiation can be important in oil-weathering, in addition to broadly-reported UV degradation. 相似文献
63.
Martínez-Alvarez R Martín N Seoane C Suárez M Pérez R Rodríguez H Kayali N 《Rapid communications in mass spectrometry : RCM》2001,15(10):758-762
The electrospray ionisation (ESI) in negative mode of the pharmacologically significant 3,5-disubstituted tetrahydro-2H-1,3,5-thiadiazin-2-thiones, and their subsequent fragmentations using an ion-trap mass spectrometer, have been investigated. Experiments on sequential product ion fragmentations (MS(n)) were performed in order to elucidate the degradation pathways for these compounds. The data presented show that the fragmentation of the even-electron [M - H](-) ions could proceed through an internal nucleophilic substitution displacement. Decarboxylation and extrusion of carbon disulfide are other fragmentations observed. 相似文献
64.
Summary Plots of capacity factor and retention time vs. elution solvent composition were proved to be useful to interpret the retention
behavior of Kepone and its metabolites in a reversed-phase solid-phase extraction and to optimize the elution solvent. The
percent recovery of Kepone was largely improved when the solvent was optimized. The standard deviations of the results of
extractions were also improved upon the optimization of the solvent. 相似文献
65.
66.
67.
68.
The reactions of HgI(2) with the semirigid ditopic ligand 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bbimms) afforded three new complexes, [Hg(2)(mu-I)(2)I(2)(bbimms)] (1), [Hg(2)I(4)(bbimms)(2)] (2), and catena-poly[HgI(2)(bbimms)] (3). The ligand and all complexes have been structurally characterized by single-crystal X-ray diffraction. 1 is a triply bridged dinuclear complex comprised of two Hg(II) ions, one bridging ligand, two bridging I(-) anions, and two terminal I(-) anions. 2 is a dinuclear metallamacrocycle comprised of two Hg(II) ions, two bridging ligands, and four terminal I(-) anions, while 3 is a helical chain with the repeating unit of HgI(2)(bbimms). 2 and 3 can be classified as supramolecular isomers, and both are related to the triply bridged precursor 1 via the addition of one more ligand in a ring-opening process. 相似文献
69.
A reaction of 5-cyano-1,3-dimethyluracil (1, R = CN) with acetone in base afforded 1,3,7-trimethylpyrido-[2,3-d]pyrimidine-2,4(1H,3H)dione ( 9a ) in a moderate yield. From a reaction mixture of 1 (R = CN) with butanone, 1,3,6,7-tetramethyl- and 7-ethyl-1,3-dimethylpyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione ( 9b and 9c , respectively) were isolated in low yields. When ethyl cyanoacetate or malononitrile was used in place of the ketone in the above reaction, 7-amino-6-ethoxycarbonyl- and 7-amino-6-cyano-1,3-dimethylpyrido[2,3-d]-pyrimidine-2,4(1H,3H)-dione ( 14a and 14b , respectively) were obtained in quantitative yields. A plausible mechanism for the formation of bicyclic compounds is discussed. 相似文献
70.
A new program to characterize polyethylene glycol-modified (PEGylated) proteins is outlined using capillary zone electrophoresis (CZE). PEGylated ribonuclease A and lysozyme were selected as examples. Five separation procedures were compared to select out the mixed buffer of acetonitrile-water (1:1, v/v) at pH 2.5 as the best to characterize the PEGylated proteins without sample pretreatment. Polyethylene oxide (PEO) with a high molecular mass of 8 x 10(6) was applied to rinse the capillary to form a dynamic coating which would decrease the undesirable proteins adsorbed to the inner wall of the silica. The electroosmotic flow (EOF) mobility of the five procedures was determined, respectively. It is found that acetonitrile is mainly responsible for the good resolution of PEGylated proteins with the help of PEO coating in the semi-aqueous system. The low EOF mobility and current in the semi-aqueous system might also have some responsibility for the high resolution. The semi-aqueous procedure described in this paper also demonstrates higher resolution of natural proteins than aqueous ones. 相似文献